ES2784742T3 - Aircraft glazing with solar control properties - Google Patents

Abstract

An aircraft glazing, comprising: a stretched acrylic layer having a first major surface and a second major surface; a topcoat formed on at least a portion of the first major surface of the layer and comprising a polysiloxane material comprising the reaction product of: (a) a hybrid copolymer comprising: (i) a first monomer comprising a hydroxy-functional organoacrylate; and (ii) a second monomer comprising an organoalkoxysilane; and (b) a second material comprising an organoalkoxysilane; and a top coat formed on at least a portion of the topcoat and comprising a silicon oxycarbide coating.

Description

DESCRIPTION

Aircraft glazing with solar control properties

Background of the invention

1. Field of the invention

This invention relates generally to aircraft glazing having solar control properties.

2. Technical considerations

Aircraft glazing, such as aircraft cabin or cabin windows, are typically made from one or more polymeric substrates mounted on a frame. Polymeric substrates are lighter than glass substrates, which decrease the overall weight of the aircraft, which in turn saves fuel. In addition, these polymeric substrates have a higher resistance to fracture than glass substrates, providing greater security. These conventional cabin windows allow passengers to see outside the plane and allow sunlight to enter the cabin. However, the transmission of solar energy through the cabin window can increase the temperature inside the cabin, which can increase the load on the aircraft's air conditioning system.

In an effort to decrease the heat load transmitted through conventional car windows, various shading devices have been developed. These can range from simple devices, such as an opaque hood that can be raised and lowered, to complex devices, such as electrochromic devices that darken with the application of electrical potential. However, these shading devices also have some drawbacks. If a passenger uses the sun visor or darkens the electrochromic device to reduce heat transfer to the cabin, the passenger can no longer enjoy the view out the window. Additionally, solar energy passing through the cab window can heat up or damage the components of the electrochromic device.

Therefore, it would be advantageous to provide an aircraft glazing, such as an aircraft cabin window, that has improved solar control properties compared to previous aircraft glazing but does not have a substantial adverse impact on passenger vision. outside the glass of the plane.

US 2007/0122598 A1 relates to duplex coatings that include a siloxane-based soft coating and a plasma-based SiOxCy coating applied to stretched acrylic substrates to improve their durability in aircraft window applications. It is mentioned that the siloxane-based soft coating is prepared as a sol-gel polysiloxane coating from mixtures of a solvent, an organosiloxane, an alkoxide and a catalyst.

WO 2009/064742 A1 refers to protection devices against electromagnetic radiation that include a first layer having a surface No. 1 and a surface No. 2 and a second layer having a surface No. 3 and a surface No. 4, where surface No. 2 of the first layer faces surface No. 3 of the second layer. A first coating is provided having three or more metallic layers on at least a part of the first layer, in particular surface No. 2, and a second coating comprising at least three metallic layers is formed on at least a part of the second layer, in particular surface No. 3.

WO 2008/127370 A2 relates to articles such as aircraft glazing, which are coated with a specific primer, the primer comprising the reaction product of a polyepoxide and an amino functional silane, wherein the reaction product, when hydrolyzed, comprises at least six silanol groups.

US 2003/0180547 A1 relates to a multi-layer solar control coating, comprising a stack of alternating anti-reflective layers and infrared reflective films.

US 2007/026235 A1 discloses a glazing system for motor vehicles including a panel that is provided on its upper side with a first protective coating system comprising a weathering layer and at least two abrasion resistant layers and on the side bottom with a second protective system comprising at least two abrasion resistant layers.

Summary of the invention

The present invention relates to a method for manufacturing aircraft glazing that is transparent, comprising the steps of: providing a stretched first acrylic layer having a first major surface and a second major surface; providing a second stretched acrylic layer having a third major surface and a fourth major surface; and providing a stack of coating that has solar control properties on at least a portion of one or more of the major surfaces. Liner stacking comprises: a first primer layer formed on at least a part of one of the main surfaces, the first primer layer comprising an amino siloxane-containing epoxy material; a solar coating formed on at least a part of the first primer layer, the solar control coating comprising at least three layers of metallic silver; a protective coating formed on at least a portion of the sun control coating, the protective coating comprising silica and alumina; a top coat formed over at least a portion of the protective coating and comprising a polysiloxane material;

and a finish coating formed on at least a portion of the top layer and comprising a diamond-like carbon-type coating. The top layer polysiloxane material comprises the reaction product of (a) a hybrid copolymer comprising (i) a first monomer comprising a hydroxyl functional organoacrylate; and (ii) a second monomer comprising an organoalkoxysilane, and (b) a second material comprising an organoalkoxysilane.

The present invention further relates to aircraft glazing, comprising a stretched acrylic layer having a first major surface and a second major surface. A finish layer is formed on at least a part of at least one major surface of the layer, for example the outer surface, and comprises a polysiloxane material. A top coat is formed over at least a part of the top coat and comprises a coating of silicon oxycarbide. The top layer comprises a polysiloxane polymer comprising the reaction product of: (a) a hybrid copolymer comprising (i) a first monomer comprising a hydroxy-functional organoacrylate and (ii) a second monomer comprising an organoalkoxysilane, and

(b) a second material comprising an organoalkoxysilane.

Brief description of the drawings

The invention will be described with reference to the following drawing figures in which like reference numerals identify like parts from start to finish.

Fig. 1 is a side sectional (not to scale) view of aircraft glazing in the form of a cockpit window assembly incorporating features of the invention;

Fig. 2 is a cross-sectional view (not to scale) of a coated car window ply of Fig. 1; Fig. 3 is a cross-sectional view (not to scale) of a solar control liner useful for the invention; Fig. 4 is a cross-sectional view (not to scale) of a portion of a coating stack incorporating features of the invention;

Fig. 5 is a cross-sectional view (not to scale) of a portion of a coating stack incorporating features of the invention;

Fig. 6 is a side sectional (not to scale) view of another non-limiting aircraft glazing of the invention in the form of a cockpit window assembly;

Fig. 7 is a cross-sectional view (not to scale) of a coated car window ply of Fig. 6; and Fig. 8 is a side sectional (not to scale) view of another non-limiting aircraft glazing of the invention in the form of a cockpit window assembly.

Description of the preferred embodiments

As used herein, spatial or directional terms, such as "left", "right", "internal", "external", "above", "below", and the like, refer to the invention as shown in the drawing figures. However, it should be understood that the invention may take various alternative orientations and, accordingly, such terms should not be construed as limiting. Furthermore, as used herein, all numbers expressing dimensions, physical characteristics, processing parameters, ingredient amounts, reaction conditions, and the like, used in the specification and claims, are to be understood as modified throughout. cases by the term "approximately". Accordingly, unless otherwise indicated, the numerical values set forth in the following specification and claims may vary depending on the desired properties that the present invention is intended to obtain. At a minimum, and not in an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should be interpreted at least in light of the number of significant digits indicated and by applying the usual rounding techniques. . Furthermore, it should be understood that all ranges disclosed in this document encompass the beginning and ending range values and any and all sub-ranges sub-included therein. For example, a set range of "1 to 10" should be considered to include any and all subranges between (and including) the minimum value of 1 and the maximum value of 10; that is, all subintervals that start with a minimum value of 1 or greater and end with a maximum value of 10 or less, for example, 1 to 3.3, 4.7 to 7.5, 5, 5 to 10 and the like.

Furthermore, as used herein, the terms "formed on", "deposited on" or "provided on" mean formed, deposited or provided on an underlying surface but not necessarily in direct contact with the surface. For example, a coating layer "formed on" a substrate does not exclude the presence of one or more different coating layers or films of the same or a different composition positioned between the formed coating layer and the substrate. As used herein, the term "film" refers to a coating region of a desired or selected coating composition.

A "layer" can comprise one or more "films". A "liner" or "liner stack" can understand one or more "layers". As used herein, the terms "polymer" or "polymeric" include oligomers, homopolymers, copolymers, and terpolymers, for example, polymers formed from two or more types of monomers or polymers. The terms "visible region" or "visible light" refer to electromagnetic radiation that has a wavelength in the range 380 nm to 780 nm. The terms "infrared region" or "infrared radiation" refer to electromagnetic radiation that has a wavelength in the range of greater than 780 nm to 100,000 nm. The terms "ultraviolet region" or "ultraviolet radiation" mean electromagnetic energy having a wavelength in the range of 100 nm to less than 380 nm.

For the purposes of the following discussion, the invention will be discussed with reference to the use of an aircraft glazing in the form of an aircraft cabin window. However, it should be understood that the invention is not limited to the use of aircraft cabin windows. Therefore, it should be understood that the specifically disclosed exemplary embodiments are presented merely to explain the general concepts of the invention and that the invention is not limited to these specific exemplary embodiments.

A non-limiting aircraft glazing 10 (eg, cockpit window assembly or cockpit window assembly) is illustrated in Fig. 1. Glazing 10 can have any desired visible light, infrared radiation, or ultraviolet radiation transmission and reflection. For example, glazing 10 can have a visible light transmission of any desired amount, eg, greater than 0% to 100% for a reference wavelength of 550 nanometers (nm). In a non-limiting embodiment, the transmission of visible light at a reference wavelength of 550 nm may be at least 20%, such as at least 30%, such as at least 40%, such as at least the 50%, such as at least 60%, such as at least 70%, such as at least 80%, such as at least 90%.

As shown in Fig. 1, glazing 10 includes a first layer 12 with a first major surface 14 facing the exterior of the aircraft, that is, an external major surface (surface No. 1) and an opposite second major surface. or internal 16 (surface No. 2). Glazing 10 also includes a second layer 18 having an outer (first) major surface 20 (No. 3 surface) and a (second) inner major surface 22 (No. 4 surface). This numbering of the layer surfaces is in keeping with conventional practice in the coating art. The first layer 12 and the second layer 18 are held in a frame assembly 24 and are separated with an air gap 26 between them. An optional electrochromic assembly 28 may be held in frame assembly 24 and separated from second layer 18. In the non-limiting embodiment shown in Fig. 1, a coating stack 30 having solar control properties, for example, incorporating a coating or solar control part, is formed on at least a part of at least one of the main surfaces, such as on surface 14 No. 1 of the first layer 12. An anti-fog panel, such as a glass panel coated with Indium tin oxide can be placed behind the second layer 18. A dust cover can be placed inside the electrochromic assembly 28.

Frame assembly 24 can be of various types known in the art. Frame assembly 24 may include a frame that surrounds a joint to maintain layers 12 and 18 in separate relationship. The frame can be made of any structurally stable material, such as, but not limited to, a plastic or metal, eg aluminum, and functional in protecting the gasket material from damage and to provide additional structural stability to the glazing 10. The space of air 26, among other things, thermal insulation ratio between the external atmosphere of the aircraft cabin and the atmosphere inside the cabin. Non-limiting examples of suitable frame assemblies 24 are described, for example, in US Patent Nos. 6,561,460 and 6,783,099.

The layers 12, 18 of glazing 10 can be of the same material or different materials and can include any desired material having any desired characteristics. For example, one or more of the sheets 12, 18 can be transparent or translucent to visible light. By "transparent" is meant a visible light transmission greater than 0% to 100%. Alternatively, one or more of the sheets 12, 18 can be translucent. By "translucent" is meant allowing electromagnetic energy (eg visible light) to pass through, but diffusing this energy so that objects on the side opposite the viewer are not clearly visible. Examples of suitable materials for layers 12, 18 include, but are not limited to, plastic substrates (such as acrylic polymers, such as polyacrylates; polyalkylmethacrylates, such as polymethylmethacrylates, polyethyl methacrylates, polypropyl methacrylates, and the like; polyurethanes; polycarbonates ; polyalkylterephthalates, such as polyethylene terephthalate (PET), polypropylene terephthalates, polybutylene terephthalates and the like; polymers containing polysiloxane; or copolymers of any monomer for the preparation of these or any mixture thereof); ceramic substrates; glass substrates; or combinations of any of the above. As discussed above, the aircraft glazing according to the present invention includes at least one stretched acrylic layer. In a non-limiting embodiment, both layers 12, 18 are made of a polymeric material, such as stretched acrylic. However, in other embodiments, one of the layers 12, 18 may be conventional soda-lime-silicate glass, borosilicate glass, lead glass, low iron glass, lithium doped glass, or alumina silicate glass. and lithium. One of the glass layers can be clear glass, that is, unstained or colorless glass, or it can be tinted or other colored glass. The glass can be annealed, heat treated, or chemically tempered glass. As used herein, the term "heat treated" means tempered or at least partially tempered. The glass can be of any type, such as conventional float glass, and can be of any composition having any optical property, for example, any visible transmission value, ultraviolet transmission, infrared transmission and / or total solar energy transmission. In the non-limiting embodiment shown in Fig. 1, the first and second layers 12, 18 are acrylic substrates, such as stretched acrylic substrates.

The first and second sheets 12, 18 can be of any desired dimension, eg, length, width, shape, or thickness. Although the dimensions of the glazing 10 are not limiting of the invention, in a non-limiting embodiment for aircraft window assemblies having overall dimensions of approximately 20 inches (51 cm) wide by 25 inches (64 cm) high and a thickness total in the range of 1.5 to 2.5 inches (3.8 to 6.4 cm), an air gap thickness 26 thicknesses in the range of 1.0 inch (2.54 cm) to 2.0 inches (5.08 cm) is acceptable.

Layers 12, 18 can be of any thickness. However, as those skilled in the art can observe, increasing the thickness of the layers 12, 18 beyond what is necessary to withstand the rigors of flight, undesirably increases the weight of the glazing 10. For example, and without limiting the present invention, for many applications, a layer thickness ranging from 0.20 to 0.40 inches (0.51 to 1.02 cm) is acceptable to withstand the rigors of flight. In a particular non-limiting embodiment, Layers 12, 18 are stretched acrylic and have a thickness ranging from 0.31 to 0.40 inches (0.79 to 1.02 cm).

The coating stack 30 having solar control properties is deposited on at least a portion of a major surface of one of the layers 12, 18. In the non-limiting embodiment shown in Fig. 1, the coating stack 30 is formed on at least a portion of the outer major surface 14 of the first (outer) layer 12. An exemplary coating stack 30 useful for the invention is shown in Fig. 2. In this non-limiting embodiment, the coating stack 30 includes a first primer layer 32, an optional first protective coating (inner) 34 (e.g., providing barrier or adhesion promoting properties), a sun control coating 36, a second protective coating (outer) 38 (for example, providing adhesion promoting properties), an optional second primer coat (exterior) 40, a top coat 42, and a second coat 44.

The primer layer 32 helps adhere the solar control coating 36 to the substrate (layer) 12 and also provides an intermediate stiffness between the substrate, eg, stretched acrylic fabric 12, and post-applied coatings. Suitable primer materials include, but are not limited to, siloxane-based primers, organosilane primers, epoxy amino siloxane primers, polysiloxane primers, and acrylic primers. Examples of suitable primer materials are described in US Patent Nos. 5,939,188; 4,670,350; 4,816,288; 4,725,501; 5,994,452; 6,110,327; and 5,776,548. Primer coat 32 can be applied in any conventional manner, such as by flow coating. In a particular non-limiting embodiment, primer layer 32 comprises a polysiloxane or epoxy amino siloxane material and has a thickness in the range of 0.1 to 10 microns, such as 0.5 to 8 microns, such as 1 to 5. microns, such as 1 to 3 microns, such as 1 to 2 microns. Alternatively, for some substrates, such as polyurethane, the primer layer 32 can be removed.

An optional first protective coating 34 can be applied over the primer layer 32. The protective coating 34 can help protect the sun control coating 36 from mechanical and / or chemical attack by any material leached from the primer layer 32 or caused by any further processing steps. The protective coating 34 can be of any desired material or mixture of materials, such as, but not limited to, one or more inorganic materials. Examples of suitable materials include, but are not limited to, metal oxides, silicon oxides, aluminum oxides, aluminosilicates, silicon nitrides, silicon carbides, and silicon oxycarbons, just to name a few. In an exemplary embodiment, protective coating 34 may include one or more metal oxide materials, such as, but not limited to, zirconium, aluminum, silicon oxides, or mixtures thereof. For example, protective coating 34 can be a single coating layer comprising alumina in the range of 0% by weight to 100% by weight and / or silica from 0% by weight to 100% by weight and / or zirconium oxide. from 0% by weight to 100% by weight. For example, the protective coating can include silica and alumina having, for example, 1% by weight to 99% by weight silica and 99% by weight to 1% by weight alumina, such as at least 70% by weight silica. and 30% by weight or less of alumina, such as at least 75% by weight of silica, such as at least 80% by weight of silica, such as at least 85% by weight of silica. In a particular non-limiting embodiment, protective coating 34 comprises 85% by weight of silica and 15% by weight of alumina. Other materials, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium and / or oxides thereof, may also be present, for example, to adjust the refractive index of the protective coating 34. In a Non-limiting embodiment, the refractive index of the protective coating 34 may be in the range of 1 to 3, such as 1 to 2, such as 1.4 to 2, such as 1.4 to 1.8.

In a non-limiting embodiment, protective coating 34 comprises a combination of silica and alumina having a thickness in the range of 5 nm to 5,000 nm, such as 5 nm to 3,000 nm, such as 5 nm to 2,000 nm, such as 5 nm to 1,000 nm, such as 10 nm to 500 nm, such as 20 nm to 300 nm, such as 50 nm to 300 nm, for example, 50 nm to 200 nm, such as 50 nm to 150 nm, such as 50 nm to 120 nm, such as 60 nm to 120 nm, such as 70 nm to 120 nm, such as 70 nm to 100 nm, such as 70 nm to 80 nm. In a particular non-limiting embodiment, the protective coating can have a thickness of at least 50 nm, such as at least 60 nm, such as at least 70 nm, such as at least 75 nm, such as at least 100 nm, such as at least 110 nm, as at least 120 nm, as at least 150 nm, as at minus 200 nm.

In another non-limiting embodiment, the protective liner 34 comprises a multilayer structure, eg, a first layer with at least one second layer formed on the first layer. In a specific non-limiting embodiment, the first layer comprises alumina or a mixture or alloy comprising alumina and silica. For example, the first layer may have more than 5% by weight of alumina, such as more than 10% by weight of alumina, such as more than 15% by weight of alumina, such as more than 30% by weight of alumina, such as more than 40% by weight alumina, such as 50% by weight to 70% by weight alumina, as in the range of 70% by weight to 100% by weight alumina and 30% by weight to 0% by weight silica , such as more than 90% by weight of alumina, such as more than 95% by weight of alumina. In a non-limiting embodiment, the first layer comprises all or substantially all of alumina. In a non-limiting embodiment, the first layer may have a thickness in the range of greater than 0 nm to 1 micron, such as 5 nm to 10 nm, such as 10 nm to 25 nm, such as 10 nm to 15 nm.

The second layer can comprise silica or a mixture or alloy comprising silica and alumina. For example, the second layer may comprise a silica / alumina mixture having more than 40% by weight of silica, such as more than 50% by weight of silica, such as more than 60% by weight of silica, such as more than 70% by weight of silica, such as more than 80% by weight of silica, such as in the range of 80% by weight to 90% by weight of silica and 10% by weight to 20% by weight of alumina, for example, 85 % by weight of silica and 15% by weight of alumina. In a non-limiting embodiment, the second layer may have a thickness in the range of greater than 0 nm to 2 microns, such as 5 nm to 500 nm, such as 5 nm to 200 nm, such as 10 nm to 100 nm, such as 30 nm to 50 nm, such as 35 nm to 40 nm. In another non-limiting embodiment, the second layer may have a thickness in the range of greater than 0 nm to 1 micron, such as 5 nm to 10 nm, such as 10 nm to 25 nm, such as 10 nm to 15 nm. In another non-limiting embodiment, protective coating 34 can be a bilayer formed by a metal oxide-containing layer (eg, a first layer containing silica and / or alumina) formed over another metal oxide-containing layer (eg, a second layer containing silica and / or alumina layer). The individual layers of the multilayer protective coating can be of any desired thickness. Non-limiting examples of suitable protective coatings are described, for example, in US Patent Application Nos. 10 / 007,382; 10 / 133,805; 10 / 397,001; 10 / 422,094; 10 / 422,095; and 10 / 422,096.

The protective coating 34 can be deposited by any conventional method, such as, but not limited to, conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of ^p V ^d processes include electron beam evaporation and vacuum sputtering (such as magnetron sputtering vacuum deposition (MSVD)). Other coating methods could also be used, such as, but not limited to, sol-gel deposition. In a non-limiting embodiment, the protective coating can be deposited by MSVD.

A sun control coating 36 is deposited on the primer layer 32 (or on the protective coating 34, if present). As used herein, the term "solar control coating" refers to a coating formed from one or more layers or films that influence the solar properties of the coated article, such as, but not limited to, the amount of solar radiation. , for example, visible radiation, infrared or ultraviolet radiation, reflected from, absorbed by, or passing through the coated article; the shading coefficient; emissivity, etc. The solar control coating 36 can block, absorb, or filter selected portions of the solar spectrum, such as, but not limited to, the IR, UV and / or visible spectra. Examples of solar control coatings that can be used in the practice of the invention are found, for example, but are not to be construed as limiting, in US Patent Nos. 4,898,789; 5,821,001; 4,716,086; 4,610,771; 4,902,580; 4,716,086; 4,806,220; 4,898,790; 4,834,857; 4,948,677; 5,059,295; and 5,028,759, and also in US Patent Application No. 09 / 058,440.

In a non-limiting embodiment, the solar control coating 36 includes one or more metallic films placed between pairs of dielectric layers. The solar control coating 36 may be a heat and / or radiation reflective coating and may have one or more coating layers or films of the same or different composition and / or functionality. For example, the solar control coating 36 can be a single layer coating or a multi-layer coating and can include one or more metals, non-metals, semimetals, semiconductors and / or alloys, compounds, compositions, combinations or mixtures of the same. For example, the solar control coating 36 may be a single layer metal oxide coating, a multi layer metal oxide coating, a non-metallic oxide coating, a metal nitride or oxynitride coating, a nitride coating or non-metallic oxynitride, or a multilayer coating comprising one or more of any of the above materials. In a non-limiting embodiment, the solar control coating 36 can be a doped metal oxide coating.

Non-limiting examples of suitable solar control coatings for use with the invention are commercially available from PPG Industries, Inc. of Pittsburgh, Pennsylvania, in the SUNGATE® and SOLARBAN® coating families. Such coatings typically include one or more anti-reflective coating films comprising dielectric or anti-reflective materials, such as metal oxides or metal alloy oxides, that are transparent to visible light. These coatings also include one or more reflective films infrared rays comprising a reflective metal, for example, a noble metal, such as gold, copper or silver, or combinations or alloys thereof, and may further comprise a sacrificial primer film or barrier film, such as titanium, such as is known in the art, placed on and / or under the metallic reflective layer. The solar control coating 36 can have any desired number of infrared reflective films, such as, but not limited to, 1 to 8 infrared reflective films. In a non-limiting embodiment, the solar control coating 36 may have 1 or more layers of metallic silver, for example 2 or more layers of silver, for example 3 or more layers of silver, such as 4 or more layers of silver, like 5 or more layers of silver, like 6 or more layers of silver. A non-limiting example of a suitable solar control coating having three layers of silver is described in US Patent Application No. 10 / 364,089 (Publication No. 2003/0180547 A1).

The solar control coating 36 can be deposited by any conventional method, such as, but not limited to, conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation, RF plasma deposition, and vacuum spraying (such as magnetron spray vapor deposition (MSVD)). Other coating methods could also be used, such as, but not limited to, sol-gel deposition. In a non-limiting embodiment, the coating can be deposited by MSVD.

A non-limiting solar control liner 36 suitable for the invention is shown in Fig. 3. This exemplary sun control coating 36 includes a base layer or dielectric first layer 50 deposited over at least a portion of the primer layer 32 (or the protective coating 34, if present). The first dielectric layer 50 may comprise one or more films of anti-reflective materials and / or dielectric materials, such as, but not limited to, metal oxides, metal alloy oxides, nitrides, oxynitrides, or mixtures thereof. The first dielectric layer 50 can be transparent to visible light. Examples of suitable metal oxides for the first dielectric layer 50 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides can have small amounts of other materials, such as manganese oxide on bismuth, tin oxide on indium, etc. Additionally, metal alloy oxides or metal mixtures, such as zinc and tin containing oxides (e.g. zinc stannate), indium tin alloy oxide, silicon nitrides, aluminum and silicon nitrides or aluminum nitrides. Furthermore, doped metal oxides can be used, such as antimony or indium doped tin oxides or nickel or boron doped silicon oxides. The first dielectric layer 50 may be a substantially monophasic film, such as a metal alloy oxide film, for example, zinc stannate, or it may be a mixture of phases composed of zinc and tin oxides or it may be composed of a plurality of metal oxide films, such as indium tin oxide, or those disclosed in US Patent Nos. 5,821,001; 4,898,789; and 4,898,790.

In the illustrated exemplary embodiment shown in Fig. 3, the first dielectric layer 50 comprises a multiple film structure having a first film 52, for example, a metal alloy oxide film, and a second film 54, for example, a metal oxide film or mixture of oxides, deposited on the first metal alloy oxide film. In a non-limiting embodiment, the first film 52 can be a zinc / tin oxide mixture or a zinc / tin alloy oxide. Zinc / tin alloy oxide can be obtained from magnetron sputtering vacuum deposition from a zinc-tin cathode which can comprise zinc and tin in proportions of 10% by weight to 90% by weight zinc and 90% by weight to 10% by weight of tin. A suitable metal alloy oxide that may be present in the first film is zinc stannate. By "zinc stannate" is meant a composition of ZnxSn-i_xO2-x (Formula 1) where "x" ranges from greater than 0 to less than 1. For example, "x" may be greater than 0 and may be any fraction or decimal greater than 0 and less than 1. For example, where x = 2/3, Formula 1 is Zn2 / 3Sn-i / 3O4 / 3, which is more commonly described as "Zn2SnO4". A film containing zinc stannate has one or more of the forms of Formula 1 in a predominant amount in the film. In a non-limiting embodiment, the first film 52 comprises zinc stannate and has a thickness in the range of 100 Angstroms (A) to 1,000 A, such as 100 A to 800 A, such as 100 A to 500 A, such as 150 A to 500 A, such as 200 A to 500 A, such as 300 A to 500 A, such as 300 A to 400 A, such as 376 A.

The second film 54 can be a film containing zinc, such as zinc oxide. The zinc oxide film can be deposited from a zinc cathode that includes one or more materials to improve sputtering characteristics. For example, the zinc cathode can include a small amount (eg, up to 10% by weight) of tin to improve sputtering. In which case, the resulting zinc oxide film would include a small percentage of tin oxide, for example up to 10% by weight of tin oxide. In this document an oxide coating sprayed by a zinc cathode having up to 10% by weight tin is referred to as a "zinc oxide" film although some tin oxide may be present. The second film 54 may have a thickness in the range of 10A to 200A, such as 20A to 200A, such as 30A to 200A, 40A to 150A, for example, 50A to 100A, such as 60A. at 100 A, such as 60 A to 80 A, such as 70 A to 80 A, such as 73 A.

A first heat and / or radiation reflective film or layer 56 is deposited on the first dielectric layer 50. The first reflective layer 56 includes a reflective metal, such as, but not limited to, metallic gold, copper, silver, or mixtures, or alloys thereof. In one embodiment, the first reflective layer 56 comprises a layer of metallic silver having a thickness in the range of 25A to 300A, for example, 50A to 300A, for example, 50A to 200A, such as 70A to 150A, such as 70A to 100A, such as 80 A to 100 A, such as 90 A to 100 A, such as 90 A.

A first sacrificial primer film 58 is deposited on the first reflective layer. The first sacrificial primer film 58 can be an oxygen scavenging material, such as titanium, which can be sacrificed during the deposition process to prevent degradation or oxidation of the first reflective layer 56 during the sputtering process or sputtering processes. subsequent heating. The oxygen scavenging material can be chosen to oxidize before the first reflective layer material 56. If titanium is used as the first primer film 58, the titanium would preferentially oxidize to titanium dioxide prior to oxidation of the silver layer. underlying. In one embodiment, the first primer film 58 is titanium having a thickness in the range of 5 A to 50 A, for example 10 A to 40 A, for example 15 A to 25 A, for example 15 A to 20 A, for example 15 A.

A second dielectric layer 60 is deposited on the first reflective layer 56 (eg, on the first sacrificial primer film 58). The second dielectric layer 60 comprises one or more metal oxide or alloy containing films, such as those described above with respect to the first dielectric layer. In the illustrated non-limiting embodiment, the second dielectric layer 60 includes a first 62, such as a metal oxide film, for example, a zinc oxide film deposited on the first sacrificial primer film 58. A second film 64, such as a metal alloy oxide film, for example a zinc stannate film, is deposited on the first zinc oxide film 62. A third film 66, such as a metal oxide film, for example another zinc oxide layer / tin, is deposited on the zinc stannate layer to form a second dielectric layer 60 of multiple films. In a non-limiting embodiment, the zinc oxide films of the second dielectric layer may have a thickness in the range of about 10 A to 200 A, eg 20 A to 150 A, eg 30 A to 100 A, For example, 40A to 80A, for example, 50A to 80A, for example, 60A to 80A, for example, 70A to 80A, such as 73A. The metal alloy oxide layer (stannate zinc) can have a thickness in the range of 100 A to 1000 A, for example 200 A to 1000 A, for example 300 A to 800 A, for example 500 A to 800 A, for example 600 A to 800 A, for example, 600 A to 700 A; for example, 631 A.

A second heat and / or radiation reflective layer 68 is deposited on the second dielectric layer 60. The second reflective layer 68 may include any one or more of the reflective materials described above with respect to the first reflective layer 56. In one embodiment there is no Limiting, the second reflective layer 68 comprises silver having a thickness in the range of 25 A to 200 A, for example 50 A to 150 A, for example 60 A to 100 A, for example 70 A to 100 A, for example, 80 A to 90 A, for example 83 A.

A second sacrificial primer film 70 can be deposited on the second reflective layer 68. The second sacrificial primer film 70 can be of any of the materials described above with respect to the first primer film 32. In a non-limiting embodiment, the Second primer film 70 includes titanium having a thickness in the range of about 5 A to 50 A, for example 10 A to 25 A, for example 15 A to 25 A, for example 15 A to 20 A, for example example, 15 A.

A third dielectric layer 72 is deposited on the second reflective layer 68 (eg, on the second sacrificial primer film 70). The third dielectric layer 72 may also include one or more metal oxide or metal alloy containing layers, as discussed above with respect to the first and second dielectric layers. In a non-limiting embodiment, the third dielectric layer 72 is a multiple film layer similar to the second dielectric layer 60. For example, the third dielectric layer 72 may include a first layer 74, such as a metal oxide layer, for example, a zinc oxide layer, a second layer 76, such as a metal alloy oxide containing layer, for example, a zinc stannate layer, and a third layer 78, such as a metal oxide layer, for example, another oxide layer zinc. In a non-limiting embodiment, the zinc oxide films of the third dielectric layer 72 may have a thickness in the range of about 10 A to 200 A, eg, 20 A to 150 A, eg, 30 A to 100 A For example, 40A to 80A, for example, 50A to 80A, for example, 60A to 80A, for example, 70A to 80A, for example, 73A. The metal alloy oxide layer (zinc stannate) may have a thickness in the range of 100 A to 1000 A, for example 200 A to 1000 A, for example 300 A to 800 A, for example 500 A to 800 A, for example 600 A at 800 A, for example, 600 A at 700 A, for example, 631 A.

A third heat and / or radiation reflective layer 80 is deposited on the third dielectric layer 72. The third reflective layer 80 can be of any of the materials discussed above with respect to the first and second reflective layers. In a non-limiting embodiment, the third reflective layer 80 comprises silver having a thickness in the range of 25 A to 200 A, for example 50 A to 150 A, for example 60 A to 100 A, for example 70 A at 100 A, for example, 80 A at 90 A, for example, 83 A.

A third sacrificial primer film 82 is deposited on the third reflective layer 80. The third primer film 82 can be any of the primer materials described above with respect to the first or second primer films. In a non-limiting embodiment, the third sacrificial primer film 82 is titanium and has a thickness in the range of 5 A to 50 A, for example 10 A to 25 A, for example 15 A to 20 A, for example 15 A.

A fourth dielectric layer 84 is deposited on the third reflective layer 80 (eg, on the third sacrificial primer film 82). The fourth dielectric layer 84 comprises one or more layers containing metal oxide or metal alloy, such as those discussed above with respect to the first, second, or third dielectric layers. In a non-limiting embodiment, the fourth dielectric layer 84 is a multi-film layer having a first layer 86, such as a metal oxide layer, for example, a zinc oxide layer, deposited on the third primer film 82, and a second layer 88, such as a metal alloy oxide layer, eg, a zinc stannate layer, deposited on the zinc oxide layer. The zinc oxide layer 86 may have a thickness in the range of 10 A to 200 A, such as 20 A to 200 A, such as 30 A to 200 A, 40 A to 150 A, for example 50 A to 100 A, as 60 A to 100 A, such as 60 A to 80 A, such as 70 A to 80 A, such as 73 A. The zinc stannate layer 88 may have a thickness in the range of 100 A to 1,000 A, such as 100 A to 500 A, such as 150 A to 500 A, for example, 200 A to 500 A, for example, 300 A to 400 A, for example, 376 A.

As shown in Figs. 2 and 3, the protective layer 38 is applied over the solar control layer 36, for example, over the fourth dielectric layer 84, to help protect the underlying layers, such as the anti-reflective layers, from mechanical and chemical attack during processing and / or to promote adherence. The protective coating 38 may be an oxygen barrier coating layer to prevent or reduce the passage of ambient oxygen to the underlying layers of the coating, such as during heating or mixing. The protective coating 38 may be the same as described below for the optional protective coating 34. In a non-limiting embodiment, the protective coating 38 comprises a combination of silica and alumina, as in the range of 80% by weight to 90%. by weight of silica and 10% by weight to 20% by weight of alumina, for example, 85% by weight of silica and 15% by weight of alumina, having a thickness in the range of 5 nm to 5,000 nm, as 5 nm to 3,000 nm, such as 5 nm to 2,000 nm, such as 5 nm to 1,000 nm, such as 10 nm to 500 nm, such as 20 nm to 300 nm, such as 50 nm to 300 nm, for example, 50 nm to 200 nm, such as 50 nm to 150 nm, such as 50 nm to 120 nm, such as 60 nm to 120 nm, such as 70 nm to 120 nm, such as 70 nm to 100 nm, such as 70 nm to 80 nm, such as 78 nm. In a particular non-limiting embodiment, the protective coating can have a thickness of at least 50 nm, such as at least 60 nm, such as at least 70 nm, such as at least 75 nm, such as at least 100 nm, such as at least 110 nm, like at least 120 nm, like at least 150 nm, like at least 200 nm.

An optional second primer layer 40 can be applied over the protective coating 38. The optional second primer layer 40 can be the same as described below for the first primer layer 32. In a particular non-limiting embodiment, the second layer Primer 40 comprises an amino siloxane epoxy material and has a thickness in the range of 0.1 to 10 microns, such as 0.5 to 8 microns, such as 1 to 7 microns, such as 1 to 5 microns, such as 1 to 3 microns.

As discussed above, according to the present invention, a specific top coat is formed on at least a portion of a major surface of the coated layer. In the exemplary embodiment shown in Fig. 2, the top coat 42 is applied over the protective coating 38 (or the optional second primer coat 40, if present). Top layer 42 provides abrasion resistance and / or resistance to cracking of substrate 12. As discussed above, in accordance with the present invention, top layer 42 comprises a polysiloxane material, comprising the reaction product of (a) a hybrid copolymer comprising (i) a first monomer comprising a hydroxy functional organoacrylate; and (ii) a second monomer comprising an organoalkoxysilane, and (b) a second material comprising an organoalkoxysilane. Suitable topcoat materials are disclosed in WO 2007/064792 A2 and US Patent Nos. 5,693,422; 6,106,605; 6,180,248; 5,401,579; and 6,469,119. Other suitable topcoat materials are commercially available from Advanced Materials and Coating Specialties under the names LensShield 500, 501, 503, 510, and 514. Topcoat 42 may have a thickness in the range of 1 to 10 microns, such as 2 to 8 microns, like 3 to 7 microns, like 4 to 6 microns, like 4 to 5 microns. The top coat can be applied by any conventional method such as flow coating.

The material for top layer 42 may incorporate a polymer having polysiloxane-based hardcoat functionality, as well as more flexible organopolymer functionality, such as, but not limited to, acrylic or epoxy functionality. The exemplary topcoat material can be prepared as follows and as described in the following examples.

A hybrid copolymer is prepared having at least two different monomer units. The hybrid copolymer is a copolymer prepared from the reaction product of (i) a first monomer comprising a hydroxyfunctional organoacrylate and (ii) a second monomer comprising an organofunctional alkoxysilane, such as a silicon alkoxide with a polymerizable group.

In a non-limiting embodiment, the first monomer comprises a hydroxyalkyl acrylate and / or a hydroxyalkyl acrylate. The alkyl part of the hydroxyalkyl acrylate can generally be represented by the formula CnH2n + 1 where n is in the range of 1-20, such as 1-10 such as 1-5. Specific examples of the first monomer include, but are not limited to, hydroxymethyl acrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.

The second monomer is an organofunctional alkoxysilane, such as an organofunctional trialkoxysilane. The alkoxide can contain alkyl or aryl groups. Silanes of the general formula RxSi (OR ') 4-x can be used, where R is an organic radical, R' is a low molecular weight alkyl radical, and x is in the range of 1 to 4. The organic radical of R can be , vinyl, methoxyethyl, 3-glycidoxypropyl, or 3-methacryloxypropyl, just to name a few. In a non-limiting embodiment, the second monomer is a trialkoxysilane of the general formula Rsí (OR ') 3, where R is a short to medium chain length organic group suitable for polymerization, such as vinyl, 3-glycidoxypropyl, or 3 -methacryloxypropyl. In a particular embodiment, the second monomer is selected from methacryloxypropyltrimethoxysilane or vinyltrimethoxysilane.

The first and second monomers combine with an appropriate catalyst, such as azobisisobutyrolnitrile (AIBN), to form a hybrid copolymer. In the broad practice of the invention, the first and second monomers can be combined in any proportion, such as 1% by weight to 99% by weight of the first monomer to 99% by weight to 1% by weight% of the second monomer on a weight basis. total monomers combined, such as 40% by weight to 90% by weight of the first monomer, such as 50% by weight to 80% by weight of the first monomer, such as 60% by weight to 80% by weight of the first monomer, such as 70 % by weight to 80% by weight of the first monomer, such as 75% by weight of the first monomer. The hybrid copolymer can be polymerized by free radical polymerization.

The second material reacts in the presence of the hybrid copolymer, for example by condensation polymerization, to form a polysiloxane polymer. This allows the second material to react with the hybrid copolymer and also polymerize with itself, for example by condensation polymerization, providing a mechanism for direct chemical bonding between the two polymeric components. The second material comprises an organoalkoxysilane. The organoalkoxysilane can be an alkylalkoxysilane or an organofunctional alkoxysilane, such as an organofunctional trialkoxysilane, or a mixture thereof. In a non-limiting embodiment, the second material is a trialkoxysilane of the general formula RSi (OR ') 3, where R is a short to medium chain length organic group such as alkyl, vinyl, phenyl, 3-glycidoxypropyl, or 3-methacryloxypropyl . In a particular embodiment, the second material is methyltrimethoxysilane.

The hybrid copolymer and the second material can be reacted by any known technique, such as a conventional condensation reaction. Examples of conventional techniques are described in US Patent Nos. 5,693,422; 5,401,579; 6,106,605; 6,180,248; and 6,469,119. The hybrid copolymer and the second material can be combined in any desired proportion, such as 1% by weight to 99% by weight of the hybrid copolymer at 99% by weight to 1% by weight of the second material based on the total weight of the hybrid copolymer and the second material, such as 5% by weight to 50% by weight of the hybrid copolymer, such as 10% by weight to 40% by weight of the hybrid copolymer, such as 10% by weight to 30% by weight of the hybrid copolymer, such as 15% by weight to 20% by weight of the hybrid copolymer, like 17% by weight of the hybrid copolymer.

The resulting hybrid copolymer (i.e., the polymer formed from the reaction of the first hybrid copolymer and the second material) can be incorporated into a coating composition that provides improved scratching, abrasion, and chemical resistance, but sufficient to resist deformation or damage. elongation of the underlying plastic substrate without cracking or sticking. Acrylic functionality provides greater weatherability and adhesion to acrylic and polycarbonate substrates compared to previous protective coatings. In the practice of the invention, forming the hybrid copolymer by copolymerizing a hydroxy functional acrylic monomer with a trialkoxysilane provides a copolymer that can undergo further hydrolysis of the alkoxy groups, resulting in a condensation reaction with the polysiloxane matrix of the coating solution. .

The hybrid copolymer need not be limited to a copolymer having two monomers, but could include three or more monomers. For example, the resulting hybrid copolymer could be a terpolymer comprising a hydroxy-functional organoacrylate, a silicon alkoxide, and a non-hydroxy-functional monomer, such as, but not limited to, methyl methacrylate or N-vinylpyrrolidone, or any monomer that undergoes radical polymerization. free. Furthermore, the hybrid copolymer is not limited to alkyl acrylates, but could incorporate other acrylic functional materials, such as, but not limited to, aromatic acrylates or halogenated acrylates, such as fluoroacrylate. Furthermore, in addition to forming hybrid organic / inorganic copolymers by copolymerizing an organic (hydroxyfunctional) acrylate or methacrylate monomer with an acrylate or methacrylate functional silicon alkoxide, said organic-inorganic hybrid copolymers can be formed by combining any organic monomer with any alkoxide compound. silicon containing a polymerizable group that can undergo the same type of polymerization reaction. 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane is a similar methacryloxypropyltrimethylsiloxy compound. For example, vinyl, alkenyl and styryl functional organosilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, p- (t-butyldimethylsiloxy) styrene, and vinyl terminated polydimethylsiloxane prepolymer can be copolymerized with organic monomers by free radical polymerization initiated by thermal or UV radiation alike. than acrylic and methacrylic functional organosilanes. In addition, epoxy and glycidoxy functional silicon alkoxides, bis [methyldimethoxysilyl) propyl] polypropylene oxide and epoxy terminated polydimethylsiloxane prepolymer can be copolymerized with organic epoxides by UV cationic polymerization or amine addition polymerization. In addition, monomers capable of undergoing condensation polymerization, copolymers of polyamide and urethane with appropriate amine functional silicon compounds, such as 1,3-bis (aminopropyl) tetramethyldisiloxane, can also be used to form hybrid polyimide. The right monomers to experiment Substitution polymerization can be combined with silicon compounds such as bis (trimethylsilyl) bisphenol A to form hybrid copolymers by substitution polymerization. As recognized by those skilled in the art, various techniques to purify the hybrid copolymer, for example, by precipitation or fractionation, can be employed to obtain hybrid copolymer materials with a narrower property distribution and thus influence the properties of the composition of coating.

The following examples illustrate various non-limiting embodiments of a topcoat material. However, it should be understood that the invention is not limited to specific examples.

Hybrid copolymer formation

Example 1

The following ingredients were combined in a glass bottle: 70 grams (g) of Dowanol PM glycol ether, 22.5 g of 2-hydroxypropyl acrylate, 7.5 g of gamma-methacryloxypropyltrimethoxysilane, and 0.06 g of azobisisobutyrolnitrile (AIBN ). The solution was degassed for 5 minutes under vacuum, purged with nitrogen gas through a sparger for 5 minutes, and placed in a nitrogen filled oven at 82 ° C (180 ° F) overnight. The mixture was stirred several times during the first hour.

Example 2

45 g of 2-hydroxypropyl acrylate, 15 g of gamma-methacryloxypropyltrimethoxysilane and 0.12 g of azobisisobutyrolnitrile (AIBN) were added to 140 g of Dowanol PM glycol ether in a glass bottle containing a magnetic stir bar. The flask was placed in an ultrasonic bath for five minutes to aid dissolution of the AIBN, degassed in a vacuum desiccator for 15 minutes, and transferred to a nitrogen purged reaction setup consisting of a 3-inch round bottom flask. 250 milliliter (ml) mouths that were fitted with a reflux condenser, heating mantle, and nitrogen sparger and heated to hold at about 80 ° C overnight under nitrogen. The reaction mixture was allowed to cool to room temperature.

Example 3

45 g of hydroxypropyl acrylate (mixed isomers), 15 g of gamma-methacryloxypropyltrimethoxysilane, and 0.12 g of azobisisobutyrolnitrile (AIBN) were added to 140 g of Dowanol PM glycol ether in a glass bottle containing a stir bar magnetic. The solution was stirred for 2-3 minutes to dissolve most of the AIBN, placed in an ultrasonic bath for five minutes, degassed in a vacuum desiccator for 30 minutes, and transferred to a nitrogen purged reaction set consisting of into a 250 ml 3 necked round bottom flask equipped with a reflux condenser, heating mantle, and nitrogen sparger. After 10 minutes of vigorous nitrogen purging through the solution, heating was started with stirring. After 45 minutes of heating, the nitrogen purge was slowed to a minimum and the temperature reached 50 ° C. The heat was increased so that the reaction temperature reached 62 ° C in another 10 minutes, 78 ° C in 20 minutes, at which time the exothermic reaction was in progress. The temperature peaked at about 107-108 ° C 15 minutes later, after which the exotherm subsided and the reaction mixture was cooled to 70 ° C. After eight hours, the heat was increased again so that the reaction mixture reached 110 ° C in 1 hour, at which time the heat was removed and the reaction mixture was allowed to cool slightly before being used to prepare a solution of coating.

Example 4

Azobisisobutyrolnitrile (AIBN) had been recrystallized three times from methanol one week before use. Similar to Example 3 above, the three ingredients were combined directly in a 500 ml 3 necked flask equipped with a reflux condenser, heating mantle, and nitrogen sparger. The gammamethacryloxypropyltrimethoxysilane was added to the hydroxypropyl acrylate, which was then added over 3 minutes to the Dowanol PM glycol ether in the round bottom flask. After five minutes of stirring at room temperature, heating was started. Twenty minutes later, the temperature of the solution had reached 50 ° C and 0.10 g of AIBN dissolved in 10-15 ml of Dowanol PM was added via syringe through a rubber septum. Forty minutes later, the temperature of the reaction mixture had reached the maximum of 119 ° C (60 minutes after the start of the reaction), after which it decreased to 83 ° C, which was maintained until the total reaction time reached 16 hours. After cooling to room temperature, the copolymer product was used to prepare a polysiloxane coating solution. Material that was not used immediately was transferred to a brown glass bottle and stored in a refrigerator. After seven weeks of refrigerated storage, the room temperature viscosity of the product solution was 61.1 centipoise (cps).

Example 5

Recrystallized azobisisobutyrolnitrile (AIBN) was recrystallized once again from methanol prior to use. Of Similar to Example 3 above, the three ingredients were combined directly in the 250 ml 3-neck flask. First, the gamma-methacryloxypropyltrimethoxysilane was added to the hydroxypropyl acrylate, and then the mixture of the two monomers was added with stirring to 130 g of Dowanol Pm glycol ether solvent (130 g) that had been purged with nitrogen in the 3-neck flask. for 2 hours. Heating started immediately, with the reaction solution reaching 56 ° C after 24 minutes, at which point 0.10 g of AIBN was added. The reaction solution reached 117 ° C 45 minutes after the start of the reaction. At about 1.25 hours of reaction time, the temperature had dropped to 43 ° C (109 ° F), at which point the heat decreased to maintain a temperature of 86 ° C overnight. After a total time of 16.5 hours from the start of the reaction, the heat was removed to allow the product to cool to room temperature in about one hour. The product was then used to prepare a polysiloxane coating solution or transferred to a brown glass bottle for refrigerated storage. After approximately 1 week of refrigerated storage, the viscosity of the product at room temperature was 130.6 cps.

Example 6

22.5 g of 2-hydroxypropyl acrylate, 7.5 g of gamma-methacryloxypropyltrimethoxysilane and 0.06 g of dimethoxy 2-phenyl acetophenone (DMPA) were added to 70.0 g of glycol ether Dowanol PM solvent in a bottle glass and placed in an ultrasonic bath until the DMPA dissolved. The solution was then degassed for 10 minutes under vacuum followed by curing for 1 hour at room temperature under nitrogen in an ELC 4001 UV curing unit. The moderately viscous solution of the copolymer product was allowed to cool to room temperature prior to use in the preparation of a coating solution.

Preparation of coating solutions

Method I: In a non-limiting method, copolymer products of the type produced in Examples 1-6 were incorporated into durable abrasion resistant coating formulations as follows. In a typical preparation, 15 g of the copolymeric product solution was added to 72 g of methyltrimethoxysilane. In a separate container, 15 g of methanol were combined with 44.1 g of Snowtex O aqueous colloidal silica sol (commercially available from Nissan Chemical) and 3.6 g of glacial acetic acid and 1 drop of concentrated nitric acid. The silane and copolymer mixture was slowly added to the aqueous silica solution with stirring. Stirring continued overnight. The solution was then diluted with 125 g of 1-propanol, 0.3 g of BYK-306 (commercially available from BYK Chemie) and 0.75 g of 25% tetramethylammonium hydroxide in methanol (commercially available from Fisher Scientific).

Method II: In an alternative non-limiting method, 15 g of the copolymer products of Examples 1-6 were combined with 72 g of methyltrimethoxysilane and 45 g of NPC-ST colloidal silica sol in glycol ether PM (commercially available from Nissan Chemical). In a separate container, 30 g of deionized water were combined with 3.6 g of glacial acetic acid and 1 drop of concentrated nitric acid. The water-acid mixture was slowly added to the silane / copolymer / silica mixture with stirring, which continued overnight. The solution was then diluted with 100 g of 1-propanol, 0.3 g of BYK-306 (commercially available from BYK Chemie) and 0.75 g of 25% tetramethylammonium hydroxide in methanol (commercially available from Fisher Scientific).

Coatings can be applied to acrylic substrates (coated or uncoated) by flow coating followed by drying in ambient air for 20-30 minutes and heat curing at 80 ° C for 4 hours.

A top coat 44 (wear resistant coat) is applied over top coat 42. Top coat 44 comprises a silicon oxycarbide coating. Examples of suitable topcoats are described in WO 2007/064792 A2. Other examples include DIAMONEX coatings, such as Everscan, Scanshield, AegisPlus and DIAMONDSHIELD® coatings, commercially available from Morgan Technical Ceramics of Allentown, Pennsylvania. The topcoat 44 may have a thickness of 1 to 10 microns, such as 1 to 8 microns, such as 2 to 6 microns, such as 3 to 6 microns, such as 4 to 5 microns. Topcoat 44 can be applied by any conventional method, such as direct ion beam deposition or RF plasma deposition.

The top coat may have a thickness, for example, in the range of 7 microns to 10 microns. An alternate embodiment 90 of a top skin 92 and top skin 44 structure for the skin stack 30 is shown in Fig. 4 (only an outer portion of the skin stack 30 is illustrated). This embodiment 90 has a first top coat 94, a protective layer 96, a second top coat 98, and a finish coat 44. The first top coat material may be the same or different than the second top coat material. As one of ordinary skill in the coating art will appreciate, forming a coating in addition to several microns by conventional flow coating techniques is very difficult. Therefore, in the embodiment 90 shown in Fig. 4, the top skin 92 is formed in two separate stages. A first top coat 94 (comprising a material as described above for the top layer) is applied by flow coating to a thickness greater than 1 micron, such as in the range of 1 micron to 5 microns. A protective coating 96 (comprising a material as described below for the protective coating, for example 85 % by weight of silica and 15% by weight of alumina) is applied by physical deposition, such as MSVD, for a thickness in the range of 10 nm to 500 nm , such as 50 nm to 200 nm, such as 50 nm to 150 nm, such as 100 nm. The second top coat layer 98 (eg, a polysiloxane or an amino siloxane epoxy material) is formed over the protective coating 96 by flow coating to a thickness greater than 1 micron, as in the range of 1 micron to 5 microns) . This technique of inserting the MSVD 96 protective liner between the two topcoat layers overcomes the problems associated with forming a single, unitary topcoat layer having a thickness greater than several microns per flow coating. Although only one topcoat 96 is shown, it should be understood that multiple topcoats / topcoat / topcoat could be present to increase the overall thickness of the coating stack. Additionally, instead of the outer coating being the finish coating 44 described above, the outermost layer could be of the protective coating material.

Shown in Fig. 5 is another alternative embodiment 100 of a topcoat and topcoat structure for the coating stack 30. In this embodiment 100, a protective coating 102 is formed between the topcoat 104 and the topcoat 106. top coat 104 (comprising a material as described above for top coat 42) is applied by flow coating for a case greater than 1 micron, as in the range of 1 micron to 5 microns. A protective coating 102 (comprising a material as described below for protective coating 34, 38, for example, 85% by weight silica and 15% by weight alumina) is applied by physical deposition, as MSVD for a thickness in the range of 10 nm to 500 nm, such as 50 nm to 200 nm, such as 50 nm to 150 nm, such as 100 nm. Topcoat 106 (comprising a material as described above for topcoat 44, for example, a DIAMONDSHIELD® coating is applied) with a thickness greater than 1 micron, such as in the range of 4 microns to 5 microns, by direct ion beam deposition or by RF plasma deposition. The formation of the protective coating 102 between the top coat 104 and the finish coat 106 provides additional protection to the underlying coating layers from chemical and / or mechanical damage.

Electrochromic assembly 28 (see Fig. 1) can include any conventional electrochromic device that changes light transmittance in response to the application or removal of an electrical potential. Examples of suitable electrochromic devices are described in US Patent Nos. 6,561,460 and 6,783,099.

Another window assembly 110 is shown in Fig. 6. This window assembly 110 is similar to that shown in Fig. 1, except that portions 30 'and 30 "of the liner stack 30 are formed on different surfaces. For example , one part 30 'can be formed on surface No. 1 (surface 14) and another part 30 "can be formed on another surface, such as surface No. 2 (surface 16) or surface No. 3 (surface twenty). In the embodiment shown in Fig. 7, the top coat 42 and the finish coat 44 as described in the first embodiment of Fig. 1 are formed on the outer surface 14 of the first layer 12. The primer layer 32, coating optional liner 34, sun control liner 36, protective liner 38, and another top liner 112 (e.g., as described above for top liner 42) are formed on inner surface 16 (or optionally on surface 20) . As will be appreciated, the alternative top coat / finish structures of Figs. 4 and / or 5 could also be incorporated in this embodiment of the invention. Alternatively, the portion 30 "of the coating stack with the solar control coating can be formed on surface # 2 or surface # 3 and the other portion 30 'can be removed.

Another embodiment 114 of the invention is shown in Fig. 8. In the previous embodiments, the first and second layers 12, 18 were separated by an air gap 26. However, in embodiment 114 shown in Fig. 8, the layers 12, 18 are laminated. In this embodiment 114, the first layer 12 and the second layer 18 are secured by an intermediate layer 116. The intermediate layer 116 can be of any desired material and can include one or more layers or layers. Intermediate layer 116 can be a polymeric or plastic material, such as polyvinylbutyral, plasticized polyvinyl chloride, or multilayer thermoplastic materials, including polyethylene terephthalate, polyurethanes, etc. Suitable interlayer materials are described, for example, but are not to be construed as limiting, in US Patent Nos. 4,287,107 and 3,762,988. Intermediate layer 116 secures the first and second layers together, provides energy absorption, reduces noise, and increases the strength of the laminated structure. Intermediate layer 116 can also be a cushioning or attenuating material as described, for example, in US Patent No. 5,796,055. Intermediate layer 116 may have a solar control coating provided thereon or incorporated or may include a colored material to reduce transmission of solar energy. In a non-limiting embodiment, the intermediate layer 116 has a thickness in the range of 0.5mm to 1.5mm, such as 0.75mm to 0.8mm. Alternatively, the liner 30 can be removed as described above with respect to Figs. 6 and 7.

Although various aspects of the invention have been described above, other variations are contemplated within the scope of the invention. For example, the glazing may comprise a top coat 42 (top coat having a hybrid polymer as described above) formed on, for example, directly on, a stretched acrylic substrate and a finish coat 44, an oxycarbon coating. of silicon, such as a DIAMONDSHIELD coating, formed on, for example, directly on top coat 42. A solar control coating, as described above, can be formed on another major surface of the substrate.

Claims (11)

1. An aircraft glazing, comprising: a stretched acrylic layer having a first major surface and a second major surface; a top coat formed on at least a part of the first major surface of the layer and comprising a polysiloxane material comprising the reaction product of: (a) a hybrid copolymer comprising: (i) a first monomer comprising a hydroxy functional organoacrylate; Y (ii) a second monomer comprising an organoalkoxysilane; Y (b) a second material comprising an organoalkoxysilane; Y a finish coat formed over at least a portion of the top coat and comprising a silicon oxycarbide coating. 2. The glazing of claim 1, comprising: a first polymeric layer having a first major surface and a second major surface; a second polymeric layer separate from the first layer and having a third major surface and a fourth major surface; Y a coating stack having solar control properties on at least a portion of one or more of the major surfaces, wherein the coating stack comprises: - a first primer layer formed on at least a part of one of the main surfaces, the first primer layer comprising a siloxane-containing material; - a solar coating formed on at least a part of the first primer layer, the solar control coating having at least one metallic layer and at least one dielectric layer; - a protective coating formed on at least a part of the solar control coating, the protective coating comprising at least one metal oxide; - a top coat formed on at least one part of the protective coating and comprising the polysiloxane material; Y - a finish coating formed on at least a part of the top coating and comprising a coating of silicon oxycarbide, wherein at least one of the first and second layers is stretched acrylic. 3. The glazing of claim 2, wherein the first and second layers are separated by an air gap, or wherein the first and second layers are laminated by an intermediate layer. The glazing of claim 2, wherein the glazing further comprises any one of: - in the coating stack, internal protective coating between the first primer layer and the solar control coating and a second primer layer between the coating protector and top coating: o - an electrochromic assembly separated from the second layer; or - a third protective layer between the top coat and the finish coat. 5. The glazing of claim 2, wherein - the primer layer comprises an amino siloxane epoxy material; or - the solar control coating comprises three or more layers of metallic silver separated by dielectric layers; or - the protective coating comprises a mixture of silica and alumina; or - the top coating comprises a multilayer structure having a first layer comprising a polysiloxane material, a second layer comprising one or more metal oxides, and a third layer comprising a polysiloxane material. 6. The glazing of claim 1, comprising: - a first stretched acrylic layer having a first main surface and a second main surface; - a second stretched acrylic layer separated from the first layer and having a third main surface and a fourth main surface; Y - a stack of cladding having solar control properties applied on at least a part of one or more of the major surfaces, wherein the coating stack comprises: - a first primer layer formed on at least a part of one of the main surfaces, the first primer layer comprising an amino siloxane-containing epoxy material; - a solar coating formed on at least a part of the first primer layer, the solar control coating comprising at least three layers of metallic silver; - a protective coating formed on at least a part of the sun control coating, the protective coating comprising silica and alumina; - a top coat formed on at least one part of the protective coating and comprising the polysiloxane material; - a finish coating formed on at least a part of the top layer and comprising a diamond-like carbon coating, and - wherein the coating stack optionally further comprises an internal protective coating between the first primer layer and the sun control coating and a second primer layer between the protective coating and the top coating. The glazing of any of claims 2 or 6, wherein the stack of cladding is formed on at least a portion of the first major surface. 8. The glazing of claim 1, wherein - the first monomer is selected from a hydroxyfunctional acrylate and / or a hydroxyalkyl acrylate, especially where the first monomer is selected from the group consisting of hydroxymethyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate; or - the second monomer is a trialkoxysilane, especially where the second monomer is selected from trialkoxysilane; methyltrimethoxysilane; and methacryloxypropyltrimethoxysilane. The glazing of claim 1, further comprising a coating stack on at least a portion of the second surface. 10. The glazing of claim 9, wherein the cladding stack comprises: - a first primer layer formed on at least a part of the second main surface, the first primer layer comprising an amino siloxane-containing epoxy material; - a solar coating formed on at least a part of the first primer layer, the solar control coating comprising at least three layers of metallic silver; Y - a protective coating formed on at least a part of the sun control coating, the protective coating comprising silica and alumina; - optionally a top coat formed on at least a part of the protective coating and comprising a polysiloxane material; - optionally a finish coating formed on at least a part of the top layer and comprising a diamond-like carbon coating. 11. A method for manufacturing aircraft glazing, comprising the steps of: - providing a first stretched acrylic layer having a first major surface and a second major surface; - providing a second stretched acrylic layer having a third main surface and a fourth main surface; Y - providing a stack of cladding having solar control properties on at least a part of one or more of the major surfaces, wherein the stack of cladding comprises: - a first primer layer formed on at least a part of one of the main surfaces, the first primer layer comprising an amino siloxane-containing epoxy material; - a solar coating formed on at least a part of the first primer layer, the solar control coating comprising at least three layers of metallic silver; - a protective coating formed on at least a part of the sun control coating, the protective coating comprising silica and alumina; - a top coating formed on at least a part of the protective coating and comprising a polysiloxane material comprising the reaction product of: (a) a hybrid copolymer comprising: (i) a first monomer comprising a hydroxy functional organoacrylate; Y (ii) a second monomer comprising an organoalkoxysilane; Y (b) a second material comprising an organoalkoxysilane; Y - a finish coating formed on at least a part of the top layer and comprising a diamond-like carbon coating.